Aryl substituted cycloalkanones

ABSTRACT

Aryl substituted tertiary carbinols, useful as anti-viral agents and insecticides, are prepared by reacting the Grignard reagent derived from an arylalkyl or arylalkenyl iodide with a dialkyl ketone or an alkyl alkenyl ketone; or by reacting an arylalkyl or arylalkenyl ketone with an alkyl- or alkenylmagnesium halide. Corresponding cyclic tertiary carbinols are also prepared via intermediate cyclic ketones.

This application is a division of copending application Ser. No.324,540, filed Jan. 17, 1973, now U.S. Pat. No. 3,878,200.

This invention relates to aryl substituted tertiary carbinols, to thepreparation thereof and to certain novel intermediates.

The compounds of the invention are of the structural formula ##STR1##wherein Y is selected from the group consisting of: ##STR2## R' islower-alkyl or lower-alkenyl of 1 to 4 carbon atoms; R" is lower-alkylof 1 to 4 carbon atoms;

n is 1 or 2;

R' and R" can be joined to form a cyclopentane or cyclohexane ring;

R is hydrogen or lower-alkyl of 1 to 4 carbon atoms; and

Ar is phenyl or phenyl substituted by 3,4-methylenedioxy or one or twomonovalent substituents selected from the group consisting oflower-alkyl of 1 to 4 carbon atoms, lower-alkoxy of 1 to 4 carbon atoms,halogen, trifluoromethyl and trifluoromethoxy.

The carbon chains of R, R', R" and Ar substituents can be straight orbranched, although primary or secondary alkyl moieties are preferred.

When two monovalent substituents are present on the phenyl ring of Ar,they can be the same or different.

Intermediates for the compounds of the invention are prepared asdescribed in the following reaction sequences. ##STR3##

In the foregoing Reaction Sequence, A, a 1-R-1-acetylcyclopropane offormula II, where R has the meaning given hereinabove, is treated withan aldehyde ArCHO in the presence of a base to give the arylvinyl1-R-cyclopropyl ketone of formula III. The latter, when treated withlithium aluminum hydride is reduced at both the carbonyl group and theolefinic linkage to give an arylethyl 1-R-cyclopropyl carbinol offormula IV. This carbinol is then treated with phosphorus tribromide inthe presence of a metal bromide such as lithium bromide to replace thehydroxy group by bromine, which product is then treated with zincbromide to effect ring opening to form an arylalkenyl bromide of formulaV. The latter with a metallic iodide is converted to the correspondingiodide of formula VI. If a compound with a saturated alkylene chain isdesired the unsaturated bromide of formula V is hydrogenated in thepresence of palladium or platinum oxide catalyst or produce a saturatedbromide of formula Va, which is in turn converted to the correspondingiodide VIa. ##STR4##

In Reaction Sequence B the arylvinyl 1-R-cyclopropyl ketone of formulaIII is treated with an alkali metal borohydride, preferably sodiumborohydride, to reduce the carbonyl group but not the olefinic linkageand provide an arylvinyl 1-R-cyclopropyl carbinol of formula VII. Byprocedures analogous to those shown in Reaction Sequence A, the carbinolof formula VII is treated with phosphorus tribromide in the presence ofa metal bromide and then with zinc bromide to give a diunsaturatedaralkyl bromide of formula VIII. The latter is then converted to thecorresponding iodide (IX).

The compounds of formula I can be prepared from the intermediatesdescribed above according to the following methods. ##STR5##

An arylalkyl halide or arylalkenyl halide of formula V, Va, VI, VIa,VIII or IX (X is Br or I) is converted to the corresponding Grignardreagent with magnesium metal by conventional means. The iodides, VI, VIaand IX are preferred because of their greater reactivity compared to thecorresponding bromides. The Grignard reagent is then treated with aketone of formula R'COR", wherein R' and R" have the meanings givenhereinabove, to form a carbinol of formula I where n is 1. ##STR6##

An iodide of formula VI, VIa or IX or a saturated bromide of formula Vais treated with the alkali metal (M) salt of a keto ester, R" COCH₂COOR°, where R" is lower-alkyl of 1 to 4 carbon atoms and R° islower-alkyl of 1 to 6 carbon atoms. The alkali metal salt is preferablythe lithium salt. The reaction takes place in an inert solvent underanhydrous conditions and produces a substituted keto ester of formula X.If the starting material is an iodide of formula VI, VIa or IX, thereaction takes place at temperatures of 20°-60° C., whereas if thestarting material is a bromide of formula Va a higher temperature, about100°-150° C. is required. The keto ester X is then hydrolyzed anddecarboxylated by heating it in aqueous alkaline medium, preferablycontaining a lower-alkanol to provide a solvent for the keto ester. Theresulting ketone of formula XI is then treated with a Grignard reagentR'MgX, wherein R' is lower-alkyl or lower-alkenyl of 1 to 4 carbon atomsand X is halogen, preferably bromine or iodine, to afford a compound offormula I where n is 2.

The intermediate ketones of formula XI are novel and constitute afurther aspect of the present invention.

The compounds of formula I where n = 2 and wherein R' and R" are joinedto form a cyclopentane or cyclohexane ring are readily preparedaccording to Method B, employing an alkali metal salt of a2-carbo-lower-alkoxycycloalkanone of the formula ##STR7## wherein m is 1or 2. Alkylation of the latter with a halide of formula Va, VI, VIa orIX affords a keto-ester of formula ##STR8## Hydrolysis anddecarboxylation of the foregoing keto ester gives a cyclic ketone of theformula ##STR9## which can be caused to react with a Grignard reagent,R'MgX, to produce a compound of formula I: ##STR10##

The intermediate ketones of formula XIV are novel and constitute afurther aspect of the present invention.

In a modification of the foregoing process the cyclic ketone of formulaXIV can be prepared by heating a halide of formula Va, VI, VIa or IXwith a cycloalkene enamine of the formula ##STR11## wherein Z and Z' arelower-alkyl groups optionally joined to form a heterocyclic ring. Thepyrrolidine enamines are preferred reactants.

Biological evaluation of the compounds of the invention has shown thatthey possess antiviral activity. They have been found to be effective invitro against one or more of a variety of viruses, including rhino-2,equine rhino, para-influenza and respiratory syncitial virus at minimalgrowth inhibitory concentrations (mic) ranging from about 0.3 to about50 micrograms per milliliter. The mic values were determined by standardserial dilution procedures.

The compounds of the invention have also been found to possesspesticidal activity against arthropod species, as indicated by testsunder simulated field conditions in a greenhouse against one or more ofthe following pest species: yellow mealworm pupae, dock beetle larvae,cabbage looper larvae, yellow fever mosquito larvae and rhodniusprolixus nymph.

The structures of the compounds of the invention were established by themodes of synthesis, by elementary analysis, and by infrared and nuclearmagnetic resonance spectral determinations.

A further aspect of the invention relates to compositions for combattingarthropods by hindering the maturation thereof which comprise aneffective amount of at least one compound of formula I in admixture witha suitable carrier or diluent, and to the method of combattingarthropods at any stage of their development by contacting them withsaid compositions.

The compositions of the invention are effective against insects at anystage of their development short of the final adult form, i.e. at theegg, larval or pupal stages. The compounds can be formulated inconventional manner as solutions, emulsions, suspensions, dusts andaerosol sprays. The pesticide compositions of the invention can containadjuvants found normally in such preparations, including water and/ororganic solvents such as acetone, dimethylformamide, sesame oil,petroleum oils, and the like. Emulsifying and surface active agents mayalso be added. Dust formulations can contain talc, diatomaceous earth,kaolin, bentonite, calcium carbonate, wood, flour, cork, carbon, and thelike. The aerosol sprays contain propellants such asdichlorodifluoromethane. The compounds of this invention can be employedas the sole pesticide component or they can be used in admixture withother compounds having similar utility. While the concentration ofactive ingredient can vary within rather wide limits, ordinarily thepesticide will comprise not more than about 10%, and preferably about 1%by weight of the composition.

A still further aspect of the invention relates to compositions forcombatting viruses which comprise an antivirally effective amount of atleast one compound of formula I in admixture with a suitable carrier ordiluent, and to the method of combatting viruses by contacting the locusof said viruses with said compositions.

The antiviral compositions are formulated by preparing a dilute solutionor suspension in an organic or aqueous-organic medium, for example ethylalcohol, acetone, dimethylsulfoxide, and the like; and are applied tothe locus to be disinfected by conventional means such as spraying,swabbing or immersing. Alternatively, the compounds can be formulated asointments or creams by incorporating them in conventional ointment orcream bases, such as alkylpolyether alcohols, cetyl alcohol, stearylalcohol and the like; as jellies by incorporating them in conventionaljelly bases such as glycerin and tragacanth; or as aerosol sprays orfoams.

The following examples will further illustrate the invention.

PREPARATION OF INTERMEDIATES A. 2-Arylvinyl cyclopropyl ketones (III)

A1. 2-(3,4-Methylenedioxyphenyl)vinyl 1-ethylcyclopropyl ketone [III; Aris 3,4-methylenedioxyphenyl, R is C₂ H₅ ].

A mixture of 33.6 g. (0.3 mole) of 1-ethylcyclopropyl methyl ketone and45 g. (0.3 mole) of piperonal in 21 ml. of ethanol was stirred at roomtemperature, and 21 ml. of 20% aqueous sodium hydroxide was addeddropwise over a period of 30-45 minutes. The mixture was warmed at40°-60° C. for 3 hours with stirring. The solution was then cooled to0°-10° C., 0.2 ml. of glacial acetic acid added, and the mixture wasextracted with ether. The ether extracts were concentrated, and theresidue dissolved in 200 ml. of 95% ethanol, which solution when cooledcaused separation of a solid product. The latter was recrystallized from150 ml. of methanol to give 39 g. of 2-(3,4-methylenedioxyphenyl)vinyl1-ethylcyclopropyl ketone, m.p. 62°-64° C.

A2. 2-(3,4-Methylenedioxyphenyl)vinyl cyclopropyl ketone [III; Ar is3,4-methylenedioxyphenyl, R is H] was prepared from8.4 g. of cyclopropylmethyl ketone and 15 g. of piperonal according to the proceduredescribed above in Preparation A1, affording 21.5 g., m.p. 85°-87° C.when recrystallized from ethanol.

A3. 2-(3,4-Methylenedioxyphenyl)vinyl 1-methylcyclopropyl ketone [III;Ar is 3,4-methylenedioxyphenyl, R is CH₃ ] was prepared from 25.6 g. of1-methylcyclopropyl methyl ketone and 39.3 g. of piperonal according tothe procedure described above in Preparation A1, affording 29.5 g. ofcrystalline product.

A4. 2-(3,4-Dimethoxyphenyl)vinyl 1-ethylcyclopropyl ketone [III; Ar is3,4-(CH₃ O)₂ C₆ H₃, R is C₂ H₅ ] was prepared from 22.4 g. of1-ethylcyclopropyl methyl ketone and 33.2 g. of veratraldehyde accordingto the procedure described above in Preparation A1, affording 20.3 g.,b.p. 156°-158° C. (0.02 mm.).

A5. 2-(4-Methoxyphenyl)vinyl cyclopropyl ketone [III; Ar is 4-CH₃ OC₆H₄, R is H] was prepared from 84.1 g. of cyclopropyl methyl ketone and136 g. of p-methoxybenzaldehyde according to the procedure describedabove in Preparation A1, affording 173.5 l g., m.p. 70°-72° C. whenrecrystallized from ethanol.

A6. 2-Phenylvinyl cyclopropyl ketone [III; Ar is C₆ H₅, R is H] wasprepared from 13.5 g. of cyclopropyl methyl ketone and 17.1 g. ofbenzaldehyde according to the procedure described above in PreparationA1, affording 23.0 g., m.p. 58°-60° C. when recrystallized from absoluteethanol.

A7. 2-(4-Chlorophenyl)vinyl cyclopropyl ketone [III; Ar is 4-ClC₆ H₄, Ris H] was prepared from 25.2 g. of cyclopropyl methyl ketone and 42 g.of p-chlorobenzaldehyde according to the procedure described above inPreparation A1, affording 31 g., m.p. 63°-65° C. when recrystallizedfrom ethanol.

A8. 2-(p-Tolyl)vinyl cyclopropyl ketone [III; Ar is 4-CH₃ C₆ H₄, R is H]was prepared from 84.1 g. of cyclopropyl methyl ketone in 120 g. ofp-tolualdehyde according to the procedure described above in PreparationA1, affording 158.7 g., colorless plates, m.p. 78°-80° C. whenrecrystallized from ethanol.

By following the procedure of Preparation A1 above,1-isopropylcyclopropyl methyl ketone or 1-butylcyclopropyl methyl ketonecan be caused to react with piperonal to give2-(3,4-methylenedioxyphenyl)vinyl 1-isopropylcyclopropyl ketone [III; Aris 3,4-methylenedioxyphenyl, R is (CH₃)₂ CH], or2-(3,4-methylenedioxyphenyl)vinyl 1-butylcyclopropyl ketone [III; Ar is3,4-methylenedioxyphenyl, R is CH₃ CH₂ CH₂ CH₂ ], respectively.

By following the procedure of Preparation A1 above, cyclopropyl methylketone can be caused to react with 3,4-dichlorobenzaldehyde,2,4-dichlorobenzaldehyde, 4-bromobenzaldehyde, 4-fluorobenzaldehyde,4-trifluoromethoxybenzaldehyde or 4-trifluoromethylbenzaldehyde to give,respectively:

2-(3,4-dichlorophenyl)vinyl cyclopropyl ketone [III; Ar is 3,4-Cl₂ C₆H₃, R is H],

2-(2,4-dichlorophenyl)vinyl cyclopropyl ketone [III; Ar is 2,4-Cl₂ C₆H₃, R is H],

2-(4-bromophenyl)vinyl cyclopropyl ketone [III; Ar is 4-BrC₆ H₄, R isH],

2-(4-fluorophenyl)vinyl cyclopropyl ketone [III; Ar is 4-FC₆ H₄, R isH],

2-(4-trifluoromethoxyphenyl)vinyl cyclopropyl ketone [III; Ar is 4-F₃COC₆ H₄, R is H], or

2-(4-trifluoromethylphenyl)vinyl cyclopropyl ketone [III; Ar is 4-F₃ CC₆H₄, R is H].

B. 2-Arylethyl cyclopropyl carbinols (IV) and 2arylvinyl cyclopropylcarbinols (VII)

B1. 2-(3,4-Methylenedioxyphenyl)ethyl 1-ethylcyclopropyl carbinol [IV;Ar is 3,4-methylenedioxyphenyl, R is C₂ H₅ ].

A suspension of 15 g. of lithium aluminum hydride in about 500 ml. oftetrahydrofuran was heated at reflux while a solution of 60 g. of2-(3,4-methylenedioxyphenyl)vinyl 1-ethylcyclopropyl ketone (PreparationA1) in 150 ml. of tetrahydrofuran was added dropwise over a period of2-3 hours. The reaction mixture was heated at reflux for 2 hours,cooled, and then water was added very cautiously. Excess anhydroussodium sulfate was added, the mixture filtered, and the filter cakewashed several times with chloroform. The combined filtrate and washingswere evaporated to dryness to give 53 g. of an oil consisting of2-(3,4-methylenedioxyphenyl)ethyl 1-ethylcyclopropyl carbinol.

B2. 2-(3,4-Methylenedioxyphenyl)ethyl cyclopropyl carbinol [IV; Ar is3,4-methylenedioxyphenyl, R is H] was prepared from 18.4 g. of2-(3,4-methylenedioxyphenyl)vinyl cyclopropyl ketone (Preparation A2)and 3.1 g. of lithium aluminum hydride according to the proceduredescribed above in Preparation B1, affording 11.5 g., b.p. 116°-122° C.(0.005 mm.), m.p. 64°-65° C. when recrystallized from ether.

B3. 2-(3,4-Methylenedioxyphenyl)ethyl 1-methylcyclopropyl carbinol [IV;Ar is 3,4-methylenedioxyphenyl, R is CH₃ ] was prepared from 23.4 g. of2-(3,4-methylenedioxyphenyl)vinyl 1-methylcyclopropyl ketone(Preparation A3) and 3.88 g. of lithium aluminum hydride according tothe procedure described above in Preparation B1, affording 18.8 g., b.p.120°-130° C. (0.003 mm.).

B4. 2-(3,4-Dimethoxyphenyl)ethyl 1-ethylcyclopropyl carbinol [IV; Ar is3,4-(CH₃ O)₂ C₆ H₃, R is C₂ H₅ ] was prepared from 15 g. of2-(3,4-dimethoxyphenyl)vinyl 1-ethylcyclopropyl ketone (Preparation A4)and 2.2 g. of lithium aluminum hydride according to the proceduredescribed above in Preparation B1, affording 10 g., b.p. 148°-150° C.(0.01 mm.).

B5. 2-(4-Methoxyphenyl)ethyl cyclopropyl carbinol [IV; Ar is 4-CH₃ OC₆H₄, R is H] was prepared from 50 g. of 2-(4-methoxyphenyl)vinylcyclopropyl ketone (Preparation A5) and 9.7 g. of lithium aluminumhydride according to the procedure described above in Preparation B1,affording 42 g., b.p. 116°-117° C. (0.05 mm.).

B6. 2-Phenylethyl cyclopropyl carbinol [IV; Ar is C₆ H₅, R is H] wasprepared from 23 g. of 2-phenylvinyl cyclopropyl ketone (Preparation A6)and 5.22 g. of lithium aluminum hydride according to the proceduredescribed above in Preparation B1, affording 18.5 g., b.p. 89°-90° C.(0.02 mm.).

B7. 2-(4-Chlorophenyl)ethyl cyclopropyl carbinol [IV; Ar is 4-ClC₆ H₄, Ris H] was prepared from 31 g. of 2-(4-chlorophenyl)vinyl cyclopropylketone (Preparation A7) and 5.87 g. of lithium aluminum hydrideaccording to the procedure described above in Preparation B1, affording23.8 g., b.p. 105°-106° C. (0.1 mm.).

B8. 2-(p-Tolyl)ethyl cyclopropyl carbinol [IV; Ar is 4-CH₃ C₆ H₄, R isH] was prepared from 158 g. of 2-(p-tolyl)vinyl cyclopropyl ketone(Preparation A8) and 33.2 g. of lithium aluminum hydride according tothe procedure described above in Preparation B1, affording 137 g., b.p.97°-98° C. (0.13 mm.).

B9. 2-(3,4-Methylenedioxyphenyl)vinyl 1-ethylcyclopropyl carbinol [VII;Ar is 3,4-methylenedioxyphenyl, R is C₂ H₅ ].

To a cold solution of 5 g. of 2-(3,4-methylenedioxyphenyl)vinyl1-ethylcyclopropyl ketone (Preparation A1) in 50 ml. of methanol wasadded in portions 1.56 g. of sodium borohydride. The mixture was stirredat room temperature for 2 hours, then diluted with water and extractedwith ether. The ether extracts were dried and concentrated to give 3.6g. of 2-(3,4-methylenedioxyphenyl)vinyl 1-ethylcyclopropyl carbinol as acolorless oil.

By replacing the 2-(3,4-methylenedioxyphenyl)vinyl 1-ethylcyclopropylketone in Preparation B1 above by a molar equivalent amount of2-(3,4-methylenedioxyphenyl)vinyl 1-isopropylcyclopropyl ketone,2-(3,4-methylenedioxyphenyl)vinyl 1-butylcyclopropyl ketone,2-(3,4-dichlorophenyl)vinyl cyclopropyl ketone,2-(2,4-dichlorophenyl)vinyl cyclopropyl ketone, 2-(4-bromophenyl)vinylcyclopropyl ketone, 2-(4-fluorophenyl)vinyl cyclopropyl ketone,2-(4-trifluoromethoxyphenyl)vinyl cyclopropyl ketone or2-(4-trifluoromethylphenyl)vinyl cyclopropyl ketone there can beobtained, respectively:

2-(3,4-methylenedioxyphenyl)ethyl 1-isopropylcyclopropyl carbinol [IV;Ar is 3,4-methylenedioxyphenyl, R is (CH₃)₂ CH],

2-(3,4-methylenedioxyphenyl)ethyl 1-butylcyclopropyl carbinol [IV; Ar is3,4-methylenedioxyphenyl, R is CH₃ CH₂ CH₂ CH₂ ],

2-(3,4-dichlorophenyl)ethyl cyclopropyl carbinol [IV; Ar is 3,4-Cl₂ C₆H₃, R is H],

2-(2,4-dichlorophenyl)ethyl cyclopropyl carbinol [IV; Ar is 2,4-Cl₂ C₆H₃, R is H],

2-(4-bromophenyl)ethyl cyclopropyl carbinol [IV; Ar is 4-BrC₆ H₄, R isH],

2-(4-fluorophenyl)ethyl cyclopropyl carbinol [IV; Ar is 4-FC₆ H₄, R isH],

2-(4-trifluoromethoxyphenyl)ethyl cyclopropyl carbinol [IV; Ar is 4-F₃COC₆ H₄, R is H], or

2-(4-trifluoromethylphenyl)ethyl cyclopropyl carbinol [IV; Ar is 4-F₃CC₆ H₄, R is H].

C. Arylalkenyl bromides (V, VIII) and arylalkyl bromides (Va)

C1. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide [V; Ar is3,4-methylenedioxyphenyl, R is C₂ H₅ ].

To a solution of 26.4 g. (0.106 mole) of2-(3,4-methylenedioxyphenyl)ethyl 1-ethylcyclopropyl carbinol in 250 ml.of ether, cooled to -30° C. under nitrogen, was added 18 ml. ofcollidine. Lithium bromide (26 g., 0.3 mole) was then added, the mixturecooled to -50° C. and 25 g. (0.09 mole) of phosphorus tribromide wasadded dropwise. The reaction mixture was stirred at -50° C. for 10minutes, allowed to warm to 0° C. over a 3 hour period and stirred at 0°C. for 3 hours. Collidine (30 ml.) was added, followed by 10 ml. ofwater. The reaction mixture was partitioned between water and ether, theether layer washed with water and sodium chloride solution, and driedover anhydrous magnesium sulfate. The ether solution was concentrated togive an oily product used directly in the following reaction.

The latter product was dissolved in about 200 ml. of anhydrous ether andadded in a fine stream to a stirred mixture of 27 g. of zinc bromide in200 ml. of ether held at -30° to -35° C. The mixture was stirred, thenallowed to warm to 0° C. during 2 hours, held there for 30 minutes, andthen allowed to warm to room temperature over a 3 hour period andstirred for 2 hours longer. The reaction mixture was partitioned betweenether and aqueous sodium chloride. The ether layer was washed threetimes with 500 ml. of water, then with sodium chloride solution, driedover anhydrous magnesium sulfate and concentrated to remove the solvent.The residue was redissolved in ether, washed with dilute aqueous sodiumbicarbonate and with sodium chloride solution, and evaporated to give 23g. of 3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide as astraw-colored oil.

C2. 6-(3,4-Methylenedioxyphenyl)-3-hexenyl bromide [V; Ar is3,4-methylenedioxyphenyl, R is H] was prepared from 11.5 g. of2-(3,4-methylenedioxyphenyl)ethyl cyclopropyl carbinol (Preparation B2),12 g. of phosphorus tribromide, 10 g. of lithium bromide and 12.7 g. ofzinc bromide according to the procedure given above in Preparation C1,affording 12.5 g. of product as an oil.

C3. 3-Methyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide [V; Ar is3,4-methylenedioxyphenyl, R is CH₃ ] was prepared from 17.6 g. of2-(3,4-methylenedioxyphenyl)ethyl 1-methylcyclopropyl carbinol(Preparation B3), 20.3 g. of phosphorus tribromide, 18.5 g. of lithiumbromide and 21 g. of zinc bromide according to the procedure given abovethe Preparation C1, affording 19 g. of product as an oil.

C4. 3-Ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl bromide [V; Ar is 3,4-(CH₃O)₂ C₆ H₃, R is C₂ H₅ ] was prepared from 16 g. of2-(3,4-dimethoxyphenyl)ethyl 1-ethylcyclopropyl carbinol (PreparationB4), 16.8 g. of phosphorus tribromide, 16.8 g. of lithium bromide and17.6 g. of zinc bromide according to the procedure given above inPreparation C1. The product was used directly in the succeeding step(Preparation D4) without isolation.

C5. 6-(4-Methoxyphenyl)-3-hexenyl bromide [V; Ar is 4-CH₃ OC₆ H₄, R isH] was prepared from 38.2 g. of 2-(4-methoxyphenyl)ethyl cyclopropylcarbinol (Preparation B5), 42.5 g. of phosphorus tribromide, 35 g. oflithium bromide and 40 g. of zinc bromide according to the proceduregiven above in Preparation C1, affording 48 g. of product as an oil.

C6. 6-Phenyl-3-hexenyl bromide [V; Ar is C₆ H₅, R is H] was preparedfrom 16.5 g. of 2-phenylethyl cyclopropyl carbinol (Preparation B6),21.5 g. of phosphorus tribromide, 17.65 g. of lithium bromide and 20.7g. of zinc bromide according to the procedure given above in PreparationC1, affording 21 g. of product as a pale yellow oil.

C7. 6-(4-Chlorophenyl)-3-hexenyl bromide [V; Ar is 4-ClC₆ H₄, R is H]was prepared from 21 g. of 2-(4-chlorophenyl)ethyl cyclopropyl carbinol(Preparation B7), 23 g. of phosphorus tribromide, 18.85 g. of lithiumbromide and 22.5 g. of zinc bromide according to the procedure givenabove in Preparation C1, affording 25.5 g. of product as an oil.

C8. 6-(p-Tolyl)-3-hexenyl bromide [V; Ar is 4-CH₃ C₆ H₄, R is H] can beprepared from 2-(p-tolyl)ethyl cyclopropyl carbinol (Preparation B8),phosphorus tribromide, lithium bromide and zinc bromide according to theprocedure given above in Preparation C1.

C9. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3,5-hexadienyl bromide [VIII;Ar is 3,4-methylenedioxyphenyl, R is C₂ H₅ ] was prepared from 3.6 g. of2-(3,4-methylenedioxyphenyl)vinyl 1-ethylcyclopropyl carbinol(Preparation B9), 3.5 g. of phosphorus tribromide, 4.5 g. of lithiumbromide and 3.5 g. of zinc bromide according to the procedure givenabove in Preparation C1, affording 2 g. of product as an oil.

C10. 6-(4-Methoxyphenyl)hexyl bromide [Va; Ar is 4-CH₃ OC₆ H₄, R is H].

A mixture of 18.6 g. of 6-(4-methoxyphenyl)-3-hexenyl bromide(Preparation C5) and 0.21 g. of platinum oxide catalyst in 200 ml. ofisopropyl alcohol was hydrogenated until 1 mole equivalent of hydrogenhad been absorbed. The product was isolated and distilled to give 12.8g. of 6-(4-methoxyphenyl)hexyl bromide, b.p. 126°-128° C. (0.04 mm.).

C11. 6-Phenylhexyl bromide [Va; Ar is C₆ H₅, R is H] was prepared byhydrogenation of 21 g. of 6-phenyl-3-hexenyl bromide (Preparation C6)according to the procedure described above in Preparation C10, affording16 g., b.p. 86°-87° C. (0.02 mm.).

C12. 6-(4-Chlorophenyl)hexyl bromide [Va; Ar is 4-ClC₆ H₄, R is H] wasprepared by hydrogenation of 25.2 g. of 6-(4-chlorophenyl)-3-hexenylbromide (Preparation C7) according to the procedure described above inPreparation C10, affording 17 g., b.p. 110°-111° C. (0.02 mm.).

C13. 6-(p-Tolyl)hexyl bromide [Va; Ar is 4-CH₃ C₆ H₄, R is H] can beprepared by hydrogenation of 6-(p-tolyl)-3-hexenyl bromide according tothe procedure described above in Preparation C10.

By replacing the 2-(3,4-methylenedioxyphenyl)ethyl 1-ethylcyclopropylcarbinol in Preparation C1 by a molar equivalent amount of2-(3,4-methylenedioxyphenyl)ethyl 1-isopropylcyclopropyl carbinol,2-(3,4-methylenedioxyphenyl)ethyl 1-butylcyclopropyl carbinol,2-(3,4-dichlorophenyl)ethyl cyclopropyl carbinol,2-(2,4-dichlorophenyl)ethyl cyclopropyl carbinol, 2-(4-bromophenyl)ethylcyclopropyl carbinol, 2-(4-fluorophenyl)ethyl cyclopropyl carbinol,2-(4-trifluoromethoxyphenyl)ethyl cyclopropyl carbinol or2-(4-trifluoromethylphenyl)ethyl cyclopropyl carbinol there can beobtained, respectively:

3-isopropyl-6-(3,4-methylenedioxyphenyl)-3hexenyl bromide [V; Ar is3,4-methylenedioxyphenyl, R is (CH₃)₂ CH],

3-butyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide [V; Ar is3,4-methylenedioxyphenyl, R is CH₃ CH₂ CH₂ CH₂ ],

6-(3,4-dichlorophenyl)-3-hexenyl bromide [V; Ar is 3,4-Cl₂ C₆ H₃, R isH],

6-(2,4-dichlorophenyl)-3-hexenyl bromide [V; Ar is 2,4-Cl₂ C₆ H₃, R isH],

6-(4-bromophenyl)-3-hexenyl bromide [V; Ar is 4-BrC₆ H₄, R is H],

6-(4-fluorophenyl)-3-hexenyl bromide [V; Ar is 4-FC₆ H₄, R is H],

6-(4-trifluoromethoxyphenyl)-3-hexenyl bromide [V; Ar is 4-F₃ COC₆ H₄, Ris H], or

6-(4-trifluoromethylphenyl)-3-hexenyl bromide [V; Ar is 4-F₃ CC₆ H₄, Ris H].

The latter products can be hydrogenated according to the procedure ofPreparation C10 to give, respectively:

3-isopropyl-6-(3,4-methylenedioxyphenyl)hexyl bromide [Va; Ar is3,4-methylenedioxyphenyl, R is (CH₃)₂ CH],

3-butyl-6-(3,4-methylenedioxyphenyl)hexyl bromide [Va; Ar is3,4-methylenedioxyphenyl, R is CH₃ CH₂ CH₂ CH₂ ],

6-(3,4-dichlorophenyl)hexyl bromide [Va; Ar is 3,4-Cl₂ C₆ H₃, R is H],

6-(2,4-dichlorophenyl)hexyl bromide [Va; Ar is 2,4-Cl₂ C₆ H₃, R is H],

6-(4-bromophenyl)hexyl bromide [Va; Ar is 4-BrC₆ H₄, R is H],

6-(4-fluorophenyl)hexyl bromide [Va; Ar is 4-FC₆ H₄, R is H],

6-(4-trifluoromethoxyphenyl)hexyl bromide [Va; Ar is 4-F₃ COC₆ H₄, R isH], or

6-(4-trifluoromethylphenyl)hexyl bromide [Va; Ar is 4-F₃ CC₆ H₄, R isH].

D. Arylalkenyl iodides (VI, IX) and arylalkyl iodides (VIa)

D1. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide [VI; Ar is3,4-methylenedioxyphenyl, R is C₂ H₅ ].

A mixture of 23 g. of 3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenylbromide (Preparation C1) and 30 g. of powdered potassium iodide in 250ml. of dimethylformamide was stirred for about 16 hours. The reactionmixture was concentrated to remove the solvent and the residuepartitioned between cyclohexane and water. The cyclohexane layer wasseparated, dried over anhydrous magnesium sulfate and evaporated to give33.0 g. of 3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide as alight yellow oil.

D2. 6-(3,4-Methylenedioxyphenyl)-3-hexenyl iodide [VI; Ar is3,4-methylenedioxyphenyl, R is H] was prepared from 12.9 g. of6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide (Preparation C2) and 7 g.of sodium iodide in 120 ml. of acetone, refluxed for three hours,affording 12.5 g. of product as an oil.

D3. 3-Methyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide [VI; Ar is3,4-methylenedioxyphenyl, R is CH₃ ] was prepared from 19.0 g. of3-methyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide (Preparation C3)and 10.5 g. of sodium iodide in 125 ml. of acetone, to give 21 g. ofproduct as a yellow oil.

D4. 3-Ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl iodide [VI; Ar is 3,4-(CH₃O)₂ C₆ H₃, R is C₂ H₅ ] was prepared from 13.8 g. of3-ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl bromide (Preparation C4) and 9g. of sodium iodide in 120 ml. of acetone, to give 15 g. of product asan oil.

D5. 6-(4-Methoxyphenyl)-3-hexenyl iodide [VI; Ar is 4-CH₃ OC₆ H₄, R isH] was prepared from 24 g. of 6-(4-methoxyphenyl)-3-hexenyl bromide(Preparation C5) and 14.75 g. of sodium iodide in 475 ml. of 2-butanone,to give 28.5 g. of product as an oil.

D6. 6-(4-Methoxyphenyl)hexyl iodide [VIa; Ar is 4-CH₃ OC₆ H₄, R is H]was prepared from 16.5 g. of 6-(4-methoxyphenyl)hexyl bromide(Preparation C10) and 9.93 g. of sodium iodide in 325 ml. of 2-butanone,to give 19.3 g. of product as a pale yellow oil.

D7. 6-Phenylhexyl iodide [VIa; Ar is C₆ H₅, R is H] was prepared from 16g. of 6-phenylhexyl bromide (Preparation C11) and 10.95 g. of sodiumiodide in 325 ml. of 2-butanone, to give 19.1 g. of product as an oil.

D8. 6-(4-Chlorophenyl)hexyl iodide [VIa; Ar is 4-ClC₆ H₄, R is H] wasprepared from 17 g. of 6-(4-chlorophenyl)hexyl bromide (Preparation C12)and 10.2 g. of sodium iodide in 325 ml. of acetone, to give 21 g. ofproduct as an oil.

D9. 6-(p-Tolyl)hexyl iodide [VIa; Ar is 4-CH₃ C₆ H₄, R is H] can beprepared from 6-(p-tolyl)hexyl bromide (Preparation C13) and sodiumiodide in acetone according to the procedure of Preparation D2 above.

D10. 3-Ethyl-6-(3,4-methylenedioxyphenyl)-3,5-hexadienyl iodide [IX; Aris 3,4-methylenedioxyphenyl, R is C₂ H₅ ] was prepared from 10 g. of3-ethyl-6-(3,4-methylenedioxyphenyl)-3,5-hexadienyl bromide (PreparationC9) and 6 g. of sodium iodide in 120 ml. of acetone, to give 10.5 g. ofproduct as an oil.

By similar procedures 3-isopropyl-6-(3,4-methylenedioxyphenyl)hexylbromide, 3-butyl-6-(3,4-methylenedioxyphenyl)hexyl bromide,6-(3,4-dichlorophenyl)hexyl bromide, 6-(2,4-dichlorophenyl)hexylbromide, 6-(4-bromophenyl)hexyl bromide, 6-(4-fluorophenyl)hexylbromide, 6-(4-trifluoromethoxyphenyl)hexyl bromide, or6-(4-trifluoromethylphenyl)hexyl bromide can be caused to react withsodium iodide or give, respectively:

3-isopropyl-6-(3,4-methylenedioxyphenyl)hexyl iodide [VIa; Ar is3,4-methylenedioxyphenyl, R is (CH₃)₂ CH],

3-butyl-6-(3,4-methylenedioxyphenyl)hexyl iodide [VIa; Ar is3,4-methylenedioxyphenyl, R is CH₃ CH₂ CH₂ CH₂ ],

6-(3,4-dichlorophenyl)hexyl iodide [VIa; Ar is 3,4-Cl₂ C₆ H₃, R is H],

6-(2,4-dichlorophenyl)hexyl iodide [VIa; Ar is 2,4-Cl₂ C₆ H₃, R is H],

6-(4-bromophenyl)hexyl iodide [VIa; Ar is 4-BrC₆ H₄, R is H],

6-(4-fluorophenyl)hexyl iodide [VIa; Ar is 4-FC₆ H₄, R is H],

6-(4-trifluoromethoxyphenyl)hexyl iodide [VIa; Ar is 4-F₃ COC₆ H₄, R isH], or

6-(4-trifluoromethylphenyl)hexyl iodide [VIa; Ar is 4-F₃ CC₆ H₄, R isH].

EXAMPLE 1

6-ethyl-3-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 1, Y is C(C₂H₅)═CHCH₂ CH₂ ].

A small portion of a solution of 15 g. of3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D1)in 20 ml. of anhydrous ether was added to 1 g. of magnesium turnings in15 ml. of anhydrous ether. A crystal of iodine was added and themagnesium crushed with a stirring rod until reaction with the iodide wasinitiated. The rest of the iodide solution was then added at such a rateto cause gentle reflux. After the addition was complete, the mixture wasstirred at room temperature for 1 hour. A solution of 3 g. of 2-butanonein 30 ml. of anhydrous ether was then added at such a rate that theether refluxed gently. The reaction mixture was stirred for 30 minutes,then 5 ml. of water was cautiously added followed by 2.3 ml. ofconcentrated sulfuric acid in 20 ml. of water. The product was extractedwith ether, the ether solution dried over anhydrous magnesium sulfateand concentrated. The residue was chromatographed on silica gel andeluted with the pentane-benzene-chloroform-ether solvent series. Thedesired product was brought out with chloroform-ether 9:1 to give 1.9 g.of 6-ethyl-3-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-3-ol as anamber liquid.

Anal. Calcd. for C₁₉ H₂₈ O₃ : C, 74.96; H, 9.27. Found: C, 74.85; H,9.26. Infrared (IR) (oil film) λ.sub.μ^(max) 3.45ms + shldrs. (CH);6.33-6.40mss, 6.74ms, 6.69ms (unsat., arom + CH). Nuclear MagneticResonance (NMR) [20% CDCl₃, internal tetramethylsilane (TMS)] δ ppm(Ratio) 6.73(3) (arom); 5.93(2) (O--CH₂ --O); 5.22(1) =CH; 0.8-2.8 (13)(CH₂ × 6, OH); 1.15, 0.93, 0.92(9)(Me singlet + Me triplet × 2).

6-Ethyl-3-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-3-ol was found tohave a minimum inhibitory concentration in vitro of 12 micrograms permilliliter against equine rhino virus.

6-Ethyl-3-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-3-ol was found tobe pesticidal against yellow fever mosquito larvae at 1.7 ppm in water;and also effective against yellow mealworm pupae (tenebrio), dock beetlelarvae and rhodnius prolixus nymph at 5-10 micrograms per insect.

By replacing the 2-butanone in the foregoing preparation by a molarequivalent amount of acetone, 1-hexen-4-one, nonan-4-one, cyclohexanoneor cyclopentanone there can be obtained, respectively:

5-ethyl-2-methyl-8-(3,4-methylenedioxyphenyl)-5-octen-2-ol [I; Ar is3,4-methylenedioxyphenyl, R' and R" are CH₃, n is 1, Y is C(C₂ H₅)═CHCH₂CH₂ ],

4,7-diethyl-10-(3,4-methylenedioxyphenyl)-1,7-decadien-4-ol [I; Ar is3,4-methylenedioxyphenyl, R' is CH₂ ═CHCH₂, R" is C₂ H₅, n is 1, Y isC(C₂ H₅)═CHCH₂ CH₂ ],

5-(n-butyl)-8-ethyl-11-(3,4-methylenedioxyphenyl)-8-undecen-5-ol [I; Aris 3,4-methylenedioxyphenyl, R' and R" are n-butyl, n is 1, Y is C(C₂H₅)═CHCH₂ CH₂ ],

1-[3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclohexanol [I; Ar is3,4-methylenedioxyphenyl, R' and R" are together (CH₂)₅, n is 1, Y isC(C₂ H₅)═CHCH₂ CH₂ ], or

1-[3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclopentanol [I; Aris 3,4-methylenedioxyphenyl, R' and R" are together (CH₂)₄, n is 1, Y isC(C₂ H₅)═CHCH₂ CH₂ ].

By replacing the 3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodidein the foregoing preparation by a molar equivalent amount of6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D2);3-methyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D3);3-ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl iodide (Preparation D4);6-(4-methoxyphenyl)-3-hexenyl iodide (Preparation D5);6-(4-methoxyphenyl)hexyl iodide (Preparation D6); 6-phenylhexyl iodide(Preparation D7); 6-(4-chlorophenyl)hexyl iodide (Preparation D8);6-(p-tolyl)hexyl iodide (Preparation D9);3-ethyl-6-(3,4-methylenedioxyphenyl)-3,5-hexadienyl iodide (PreparationD10); 3-isopropyl-6-(3,4-methylenedioxyphenyl)hexyl iodide;3-butyl-6-(3,4-methylenedioxyphenyl)hexyl iodide,6-(3,4-dichlorophenyl)hexyl iodide; 6-(2,4-dichlorophenyl)hexyl iodide;6-(4-bromophenyl)hexyl iodide; 6-(4-fluorophenyl)hexyl iodide;6-(4-trifluoromethoxyphenyl)hexyl iodide; or6-(4-trifluoromethylphenyl)hexyl iodide, there can be obtained,respectively:

3-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 1, Y is CH═CHCH₂CH₂ ];

3,6-dimethyl-9-(3,4-methylenedioxyphenyl)-6-nonen-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 1, Y isC(CH₃)═CHCH₂ CH₂ ];

6-ethyl-3-methyl-9-(3,4-dimethoxyphenyl)-6-nonen-3-ol [I; Ar is 3,4-(CH₃O)₂ C₆ H₃, R' is C₂ H₅, R" is CH₃, n is 1, Y is C(C₂ H₅)═CHCH₂ CH₂ ];

3-methyl-9-(4-methoxyphenyl)-6-nonen-3-ol [I; Ar is 4-CH₃ OC₆ H₄, R' isC₂ H₅, R" is CH₃, n is 1, Y is CH═CHCH₂ CH₂ ];

3-methyl-9-(4-methoxyphenyl)nonan-3-ol [I; Ar is 4-CH₃ OC₆ H₄, R' is C₂H₅, R" is CH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-9-phenylnonan-3-ol [I; Ar is C₆ H₅, R' is C₂ H₅, R" is CH₃, nis 1, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-9-(4-chlorophenyl)nonan-3-ol [I; Ar is 4-ClC₆ H₄, R' is C₂ H₅,R" is CH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-9-(p-tolyl)nonan-3-ol [I; Ar is 4-CH₃ C₆ H₄, R' is C₂ H₅, R" isCH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-6-ethyl-9-(3,4-methylenedioxyphenyl)-6,8-nonadien-3-ol [I; Aris 3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 1, Y is C(C₂H₅)═CHCH═CH];

3-methyl-6-isopropyl-9-(3,4-methylenedioxyphenyl)nonan-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 1, Y isCH(isopropyl)CH₂ CH₂ CH₂ ];

3-methyl-6-butyl-9-(3,4-methylenedioxyphenyl)nonan-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 1, Y isCH(n-butyl)CH₂ CH₂ CH₂ ];

3-methyl-9-(3,4-dichlorophenyl)nonan-3-ol [I; Ar is 3,4-Cl₂ C₆ H₃, R' isC₂ H₅, R" is CH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-9-(2,4-dichlorophenyl)nonan-3-ol [I; Ar is 2,4-Cl₂ C₆ H₃, R' isC₂ H₅, R" is CH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-9-(4-bromophenyl)nonan-3-ol [I; Ar is 4-BrC₆ H₄, R' is C₂ H₅,R" is CH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-9-(4-fluorophenyl)nonan-3-ol [I; Ar is 4-FC₆ H₄, R' is C₂ H₅,R" is CH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-9-(4-trifluoromethoxyphenyl)nonan-3-ol [I; Ar is 4-F₃ COC₆ H₄,R' is C₂ H₅, R" is CH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ]; or

3-methyl-9-(4-trifluoromethylphenyl)nonan-3-ol [I; Ar is 4-F₃ CC₆ H₄, R'is C₂ H₅, R" is CH₃, n is 1, Y is CH₂ CH₂ CH₂ CH₂ ].

The foregoing iodide reactants can if desired, be replaced by thecorresponding bromides.

EXAMPLE 2

(a) Ethyl 2-acetyl-5-ethyl-8-(3,4-methylenedioxyphenyl)-5-octenoate [X;R" is CH₃, R° is C₂ H₅, Ar is 3,4-methylenedioxyphenyl, Y is C(C₂H₅)═CHCH₂ CH₂ ].

A mixture of 10 g. of the lithium salt of ethyl acetoacetate (preparedfrom ethyl acetoacetate and n-butyllithium) and 9.6 g. of3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D1)in 100 ml. of tetramethylurea was heated at 60° C. for 5 days. Thereaction mixture was filtered, the filtrate concentrated in vacuo to avolume of about 20 ml., then diluted with 200 ml. of water and extractedwith ether. The ether solution was washed with water and saturatedsodium chloride solution, and dried over anhydrous magnesium sulfate.The dried ether solution was concentrated to remove the solvent and theresidue was chromatographed on silica gel. The chromatograph column waseluted with pentane-benzene-ether solvent series which first removedunreacted iodide and then brought out the desired product, 2.4 g. ofethyl 2-acetyl-5-ethyl-8-(3,4-methylenedioxyphenyl)-5-octenoate as ayellow oil.

Anal. Calcd. for C₂₀ H₂₈ O₅ : C, 69.98; H, 7.83. Found: C, 69.97; H,7.86. IR (oil film) λ.sub.μ^(max) 3.45mss + shldrs. (CH), 5.78mss, 5.86s(C═O); 6.15-6.30m, 6.67mss, 6.73s, 6.95mss (arom and CH). NMR (20%CDCl₃, internal TMS) δ ppm (Ratio) 6.63(3) (arom); 5.86(2) (O--CH₂ --O);5.10(1) (═CH); 4.17(2) (OCH₂ quartet); 3.33(1) [(O═C)₂ --CH];1.7-2.8(13) (aliph. CH incl. COCH₃); 1.25(3), 0.90(3) (Me triplet × 2).

(b) 6-Ethyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one [XI; R" is CH₃,Ar is 3,4-methylenedioxyphenyl, Y is C(C₂ H₅)═CHCH₂ CH₂ ].

A mixture of 31.5 g. (0.0875 mole) of ethyl2-acetyl-5-ethyl-8-(3,4-methylenedioxyphenyl)-5-octenoate and 7.28 g.(0.13 mole) of potassium hydroxide in 100 ml. of methanol and 20 ml. ofwater was heated at reflux for 4 hours. An additional 7.28 g. ofpotassium hydroxide in 9 ml. of water was added and the mixture heatedat reflux for about 16 hours under nitrogen. The reaction mixture wasadded to 100 ml. of water, cooled to 0°, acidified with 5% sulfuric acidand extracted three times with 250 ml. of ether. The ether layers werewashed with dilute sodium bicarbonate and water, dried over anhydrousmagnesium carbonate and concentrated to give 27 g. of yellow oil. Thelatter was chromatographed on 160 g. of silica gel and the column elutedwith the pentane-benzene-ether solvent series. Benzene-ether 9:1 broughtout the desired product, 8 g. of6-ethyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one as a light yellowoil.

Anal. Calcd. for C₁₈ H₂₄ O₃ : C, 75.23; H, 8.06. Found: C, 74.77; H,8.34. IR (oil film) λ.sub.μ^(max) 3.45s + shldrs. (CH); 5.86s (C═O);6.24m, 6.67s, 6.74s, 6.95s (arom + CH). NMR (20% CDCl₃, internal TMS) δppm (Ratio) 6.78(3) (arom); 5.97(2) (O--CH₂ --O); 5.22(1) (--CH--),1.5-2.9(15) (CH₂ × 6, C═O--CH₃); 0.96(3) (Me triplet).

6-Ethyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one was found to have aminimum inhibitory concentration in vitro of 6-12 micrograms permilliliter against equine rhino virus.

6-Ethyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one was found to bepesticidal against dock beetle larvae at 5 micrograms per insect.

(c) 7-Ethyl-3-methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol [I; Aris 3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 2, Y is C(C₂H₅)═CHCH₂ CH₂ ].

To 14.3 g. (0.05 mole) of6-ethyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one in 200 ml. ofanhydrous ether was added 30 ml. (0.1 mole) of ethylmagnesium bromide(10 ml. of 3N ethereal solution) at -15° C. over a period of 5 minutes.The reaction mixture was allowed to warm to room temperature, stirredthere for 90 minutes and then heated at reflux for 1 hour. The reactionmixture was cooled, 21 ml. of saturated ammonium chloride solution wasadded, and the mixture extracted twice with 250 ml. portions of ether.The ether solution was dried over anhydrous magnesium sulfate andconcentrated to give 14.5 g. of oil. The latter was chromatographed on180 g. of silica gel and the column eluted with thepentane-benzene-chloroform solvent series. The material brought out bybenzene and benzene-chloroform mixtures was rechromatographed on 120 g.of silica gel. Elution with benzene containing 10-50% chloroformprovided 3.1 g. of7-ethyl-3-methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol as a yellowoil.

Anal. Calcd. for C₂₀ H₃₀ O₃ : C, 75.43; H, 9.49. Found: C, 75.91; H,9.68. IR (oil film ) λ.sub.μ^(max) 2.92m + shldrs. (OH); 3.40s + shldrs.(CH); 6.24m, 6.65mss, 6.71s, 6.94mss + shldrs. (arom, CH). NMR (20%CDCl₃, internal TMS) δ ppm (Ratio) 6.77(3) arom; 5.93(2) (O--CH₂ --O);5.20(1) (═CH--); 1.25-2.85(15) (CH₂ × 7 + OH); 1.12, 0.92, 0.88 (Mesinglet, Me triplet × 2).

7-Ethyl-3-methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol was found tohave a minimum inhibitory concentration in vitro against rhino-2, equinerhino, para-influenza and respiratory syncitial virus of 0.3, 6, 12 and6 micrograms per milliliter, respectively.

7-Ethyl-3-methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol was found tobe pesticidal against yellow mealworm pupae (tenebrio) and rhodniusprolixus nymph at 10 micrograms per insect.

EXAMPLE 3

8-ethyl-4-methyl-11-(3,4-methylenedioxyphenyl)-1,8-undecadien-4-ol [I;Ar is 3,4-methylenedioxyphenyl, R' is CH═CHCH₂, R" is CH₃, n is 2, Y isC(C₂ H₅)═CHCH₂ CH₂ ] was prepared from 6 g. of6-ethyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one (Example 2, part b)and allylmagnesium bromide (0.1 mole in 250 ml. of ether) according tothe procedure described above in Example 2. The product waschromatographed on 100 g. of silica gel, and the column was eluted withpentane containing increasing amounts of benzene and finally withbenzene alone. The later fractions brought out the desired product,8-ethyl-4-methyl-11-(3,4-methylenedioxyphenyl)-1,8-undecadien-4-ol as ayellow oil.

Anal. Calcd. for C₂₁ H₃₀ O₃ : C, 76.32; H, 9.15. Found: C, 75.50; H,9.09. IR (oil film) λ.sub.μ^(max) 2.94mms + shldrs. (OH); 3.45s +shldrs. (CH); 6.11m, 6.24m, 6.66s, 6.72s, 6.94s (unsat. arom, CH). NMR(20% CDCl₃, internal TMS) δ ppm (Ratio) 6.75(3) (arom); 5.93(2) (O--CH₂--O); 4.9-6.3(4) (CH₂ ═CH--, ═CH); 1.3-2.8(15) (CH₂ × 7 + OH); 1.15,0.92(6) (Me singlet, Me triplet).

8-Ethyl-4-methyl-11-(3,4-methylenedioxyphenyl)-1,8-undecadien-4-ol wasfound to have a minimum inhibitory concentration in vitro against equinerhino virus of 12 micrograms per milliliter.

8-Ethyl-4-methyl-11-(3,4-methylenedioxyphenyl)-1,8-undecadien-4-ol wasfound to be pesticidal against yellow mealworm pupae (tenebrio) andrhodnius prolixus nymph at 10 micrograms per insect.

EXAMPLE 4

6-ethyl-2-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-ol [I; Ar is3,4-methylenedioxyphenyl, R' and R" are CH₃, n is 2, Y is C(C₂ H₅)═CHCH₂CH₂ ] was prepared from 14.3 g. of6-ethyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one (Example 2, part b)and methylmagnesium bromide (66 ml. of 3 molar in tetrahydrofuran)according to the procedure described above in Example 2. The product (14g. of oil) was chromatographed twice on activated magnesium silicate andthe column was eluted with pentane containing increasing amounts ofbenzene. The later fractions brought out the desired product,6-ethyl-2-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-ol as a lightyellow oil.

Anal. Calcd. for C₁₉ H₂₈ O₃ : C, 74.95; H, 9.27. Found: C, 75.07; H,9.29. IR (oil film) λ.sub.μ^(max) 2.95m (OH); 3.40mss + shldrs. (CH),6.22m, 6.65mss, 6.71s, 6.92mss (arom, CH). NMR (20% CDCl₃, internal TMS)δ ppm (Ratio) 6.68(3) (arom); 5.90(2) (O--CH₂ --O); 5.13(1) (═CH);1.3-2.8(13) (CH₂ × 6 + OH); 1.2(6) (CMe₂); 0.92(3) (Me triplet).

6-Ethyl-2-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-ol was found tohave a minimum inhibitory concentration in vitro against equine rhinovirus of 12 micrograms per milliliter.

6-Ethyl-2-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-ol was found tobe pesticidal against yellow mealworm pupae (tenebrio) at 1 microgramper insect and against rhodnius prolixus nymph at 3 micrograms perinsect.

EXAMPLE 5

(a) Ethyl 2-acetyl-8-(3,4-methylenedioxyphenyl)-5-octenoate [X; R" isCH₃, R° is C₂ H₅, Ar is 3,4-methylenedioxyphenyl, Y is CH═CHCH₂ CH₂ ].

A mixture of 28.3 g. (0.1 mole) of6-(3,4-methylenedioxyphenyl)-3-hexenyl bromide and 21 g. (0.15 mole) oflithium ethylacetoacetate in 200 ml. of dimethylformamide was heatedunder nitrogen with stirring at 55°-60° C. for 2 days. The reactionmixture was concentrated in vacuo and the residue partitioned betweenwater and methylene dichloride. The methylene dichloride layer waswashed with 5% aqueous sulfuric acid, water, 5% aqueous sodiumbicarbonate and water, and dried over anhydrous magnesium sulfate. Theether solution was concentrated to afford ethyl2-acetyl-8-(3,4-methylenedioxyphenyl)-5-octenoate as a yellow oil, useddirectly in the following reaction.

(b) 9-(3,4-Methylenedioxyphenyl)-6-nonen-2-one [XI; R" is CH₃, Ar is3,4-methylenedioxyphenyl, Y is CH═CHCH₂ CH₂ ] was prepared from 27 g. ofethyl 2-acetyl-8-(3,4-methylenedioxyphenyl)-5-octenoate and potassiumhydroxide in aqueous methanol according to the procedure described abovein Example 2, part (b). The neutral fraction of the product waschromatographed on 390 g. of activated magnesium silicate and the columnwas eluted with pentane containing increasing amounts of benzene. Thelater fractions brought out the desired product, 12.3 g. of9-(3,4-methylenedioxyphenyl)-6-nonen-2-one.

(c) 3-Methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 2, Y is CH═CHCH₂CH₂ ] was prepared from 12.3 g. of9-(3,4-methylenedioxyphenyl)-6-nonen-2-one and 66 ml. of ethylmagnesiumbromide (3 molar in ether) according to the procedure described above inExample 2. The product was chromatographed on 330 g. of activatedmagnesium silicate and the column was eluted with pentane containingincreasing amounts of benzene. The later fractions brought out thedesired product, 7.8 g. of3-methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol as a pale yellowoil.

Anal. Calcd. for C₁₈ H₂₆ O₃ : C, 74.44; H, 9.02. Found: C, 74.83; H,9.03. IR (oil film) λ .sub.μ^(max) 2.95mss + shldrs. (OH); 3.45s +shldrs. (CH); 6.15m, 6.24mms, 6.66s, 6.73s, 6.95s + shldrs. (unsat.arom, CH).

EXAMPLE 6

(a) Ethyl 2-propionyl-5-ethyl-8-(3,4-methylenedioxyphenyl)-5-octenoate[X; Ar is 3,4-methylenedioxyphenyl, R" and R° are C₂ H₅, Y is C(C₂H₅)═CHCH₂ CH₂ ] was prepared from 10 g. of3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D1)and 4.6 g. of the lithium salt of ethyl 3-oxovalerate in 100 ml. ofdimethylformamide by the procedure described above in Example 2, part(a). The product was chromatographed on silica gel and diluted withchloroform containing 20% benzene to give 5.5 g. of ethyl2-propionyl-5-ethyl-8-(3,4-methylenedioxyphenyl)5-octenoate as an amberliquid.

(b) 7-Ethyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-one [XI; R" is C₂H₅, Ar is 3,4-methylenedioxyphenyl, Y is C(C₂ H₅)═CHCH₂ CH₂ ] can beprepared from ethyl2-propionyl-5-ethyl-8-(3,4-methylenedioxyphenyl)-5-octenoate andpotassium hydroxide in aqueous methanol according to the proceduredescribed in Example 2, part (b).

(c) 7-Ethyl-3-isopropyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol [I;Ar is 3,4-methylenedioxyphenyl, R' is CH(CH₃)₂, R" is C₂ H₅, n is 2, Yis C(C₂ H₅)═CHCH₂ CH₂ ] can be prepared from7-ethyl-10(3,4-methylenedioxyphenyl)-7-decen-3-one andisopropylmagnesium bromide according to the procedure described inExample 2, part (c).

EXAMPLE 7

(a) Ethyl 2-butyryl-5-ethyl-8-(3,4-methylenedioxyphenyl)-5-octenoate [X;Ar is 3,4-methylenedioxphenyl, R" is CH₂ CH₂ CH₃, R° is C₂ H₅, Y is C(C₂H₅)═CHCH₂ CH₂ ] was prepared from 20 g. of3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D1)and 12 g. of the lithium salt of ethyl 3-oxohexanoate according to theprocedure described above in Example 2. There was thus obtained 11.57 g.of ethyl 2-butyryl-5-ethyl-8-(3,4-methylenedioxyphenyl)-5-octenoate as alight yellow oil.

Anal. Calcd. for C₂₃ H₃₂ O₅ : C, 71.11; H, 8.30. Found: C, 70.89; H,8.54. IR (oil film) λ.sub.μ^(max) 3.45mss + shldrs. (CH); 5.78mss, 5.91s(C═O); 6.24m, 6.75mss, 6.68 shldr. 6.96mss (arom and CH). NMR (20%CDCl₃, internal TMS) δ ppm (Ratio) 6.73(3) (arom); 5.93(2) (O--CH₂ --O);5.17(1) (═CH); 4.22(2) (OCH₂ CH₃ quartet); 3.42(1⁺) [(O═C)₂ CH],0.7-2.8(23) (aliph. CH incl. Me triplet × 3).

(b) 8-Ethyl-11-(3,4-methylenedioxyphenyl)-8-undecen-4-one [XI; R" is CH₂CH₂ CH₃, Ar is 3,4-methylenedioxyphenyl, Y is C(C₂ H₅)═CHCH₂ CH₂ ] canbe prepared from ethyl2-butyryl-5-ethyl-8-(3,4-methylenedioxyphenyl)-5-octenoate and potassiumhydroxide in aqueous methanol according to the procedure described inExample 2, part (b).

(c) 3-Allyl-8-ethyl-11-(3,4-methylenedioxyphenyl)-8-undecen-4-ol [I; Aris 3,4-methylenedioxyphenyl, R' is CH₂ CH═CH₂, R" is CH₂ CH₂ CH₃, n is2, Y is C(C₂ H₅)═CHCH₂ CH₂ ] can be prepared from8-ethyl-11-(3,4-methylenedioxyphenyl)-8-undecen-4-one and allylmagnesiumbromide according to the procedure described in Example 2, part (c).

By replacing the 3-ethyl-6-(3,4-methylenedioxyphenyl)3-hexenyl iodide inExample 2, part (a), by a molar equivalent amount of6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D2);3-methyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide (Preparation D3);3-ethyl-6-(3,4-dimethoxyphenyl)-3-hexenyl iodide (Preparation D4);6-(4-methoxyphenyl)-3-hexenyl iodide (Preparation D5);6-(4-methoxyphenyl)hexyl iodide (Preparation D6); 6-phenylhexyl iodide(Preparation D7); 6-(4-chlorophenyl)hexyl iodide (Preparation D8);6-(p-tolyl)hexyl iodide (Preparation D9);3-ethyl-6-(3,4-methylenedioxyphenyl)-3,5-hexadienyl iodide (PreparationD10); 3-isopropyl-6-(3,4-methylenedioxyphenyl)hexyl iodide;3-butyl-6-(3,4-methylenedioxyphenyl)hexyl iodide;6-(3,4-dichlorophenyl)hexyl iodide; 6-(2,4-dichlorophenyl)hexyl iodide;6-(4-bromophenyl)hexyl iodide; 6-(4-fluorophenyl)hexyl iodide;6-(4-trifluoromethoxyphenyl)hexyl iodide; or6-(4-trifluoromethylphenyl)hexyl iodide and then carrying out thehydrolytic procedure of step (b) of Example 2, there can be obtained,respectively:

9-(3,4-methylenedioxyphenyl)-6-nonen-2-one [XI; R" is CH₃, Ar is3,4-methylenedioxyphenyl, Y is CH═CHCH₂ CH₂ ];

6-methyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one [XI; R" is CH₃, Aris 3,4-methylenedioxyphenyl, Y is C(CH₃)═CHCH₂ CH₂ ];

6-ethyl-9-(3,4-dimethoxyphenyl)-6-nonen-2-one [XI; R" is CH₃, Ar is3,4-(CH₃ O)₂ C₆ H₃, Y is C(C₂ H₅)═CHCH₂ CH₂ ];

9-(4-methoxyphenyl)-6-nonen-2-one [XI; R" is CH₃, Ar is 4-CH₃ OC₆ H₄, Yis CH═CHCH₂ CH₂ ];

9-(4-methoxyphenyl)nonan-2-one [XI; R" is CH₃, Ar is 4-CH₃ OC₆ H₄, Y isCH₂ CH₂ CH₂ CH₂ ];

9-phenylnonan-2-one [XI; R" is CH₃, Ar is C₆ H₅, Y is CH₂ CH₂ CH₂ CH₂ ];

9-(4-chlorophenyl)nonan-2-one [XI; R" is CH₃, Ar is 4-CIC₆ H₄, Y is CH₂CH₂ CH₂ CH₂ ];

9-(p-tolyl)nonan-2-one [XI; R" is CH₃, Ar is 4-CH₃ C₆ H₄, Y is CH₂ CH₂CH₂ CH₂ ];

6-ethyl-9-(3,4-methylenedioxyphenyl)-6,8-nonadien-2-one [XI; R" is CH₃,Ar is 3,4-methylenedioxphenyl, Y is C(C₂ H₅)═CHCH═CH];

6-isopropyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one [XI; R" is CH₃,Ar is 3,4-methylenedioxyphenyl, Y is C(iso-Pr)═CHCH₂ CH₂ ];

6-butyl-9-(3,4-methylenedioxyphenyl)-6-nonen-2-one [XI; R" is CH₃, Ar is3,4-methylenedioxyphenyl, Y is C(n-Bu)═CHCH₂ CH₂ ];

9-(3,4-dichlorophenyl)nonan-2-one [XI; R" is CH₃, Ar is 3,4-Cl₂ C₆ H₃, Yis CH₂ CH₂ CH₂ CH₂ ];

9-(2,4-dichlorophenyl)nonan-2-one [XI; R" is CH₃, Ar is 2,4-Cl₂ C₆ H₃, Yis CH₂ CH₂ CH₂ CH₂ ];

9-(4-bromophenyl)nonan-2-one [XI; R" is CH₃, Ar is 4-BrC₆ H₄, Y is CH₂CH₂ CH₂ CH₂ ];

9-(4-fluorophenyl)nonan-2-one [XI; R" is CH₃, Ar is 4-FC₆ H₄, Y is CH₂CH₂ CH₂ CH₂ ];

9-(4-trifluoromethoxyphenyl)nonan-2-one [XI; R" is CH₃, Ar is 4-F₃ COC₆H₄, Y is CH₂ CH₂ CH₂ CH₂ ]; or

9-(4-trifluoromethylphenyl)nonan-2-one [XI; R" is CH₃, Ar is 4-F₃ CC₆H₄, Y is CH₂ CH₂ CH₂ CH₂ ].

The foregoing ketones of formula XI can be caused to react withethylmagnesium bromide according to the procedure of Example 2, part (c)to produce the following carbinols, respectively:

3-methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 2, Y is CH═CHCH₂CH₂ ];

3,7-dimethyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 2, Y isC(CH₃)═CHCH₂ ];

7-ethyl-3-methyl-10-(3,4-dimethoxyphenyl)-7-decen-3-ol [I; Ar is3,4-(CH₃ O)₂ C₆ H₃, R' is C₂ H₅, R" is CH₃, n is 2, Y is C(C₂ H₅)═CHCH₂CH₂ ];

3-methyl-10-(4-methoxyphenyl)-7-decen-3-ol [I; Ar is 4-CH₃ OC₆ H₄, R' isC₂ H₅, R" is CH₃, n is 2, Y is CH═CHCH₂ CH₂ ];

3-methyl-10-(4-methoxyphenyl)decan-3-ol [I; Ar is 4-CH₃ OC₆ H₄, R' is C₂H₅, R" is CH₃, n is 2, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-10-phenyldecan-3-ol [I; Ar is C₆ H₅, R' is C₂ H₅, R" is CH₃, nis 2, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-10-(4-chlorophenyl)decan-3-ol [I; Ar is 4-CIC₆ H₄, R' is C₂ H₅,R" is CH₃, n is 2, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-10-(p-tolyl)decan-3-ol [I; Ar is 4-CH₃ C₆ H₄, R' is C₂ H₅, R"is CH₃, n is 2, Y is CH₂ CH₂ CH₂ CH₂ ];

7-ethyl-3-methyl-10-(3,4-methylenedioxyphenyl)-7,9-decadien-3-ol [I; Aris 3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 2, Y is C(C₂H₅)═CHCH═CH];

7-isopropyl-3-methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol [I; Aris 3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 2, Y isC(iso-Pr)═CHCH₂ CH₂ ];

7-butyl-3-methyl-10-(3,4-methylenedioxyphenyl)-7-decen-3-ol [I; Ar is3,4-methylenedioxyphenyl, R' is C₂ H₅, R" is CH₃, n is 2, Y isC(n-Bu)═CHCH₂ CH₂ ];

3-methyl-10-(3,4-dichlorophenyl)decan-3-ol [I; Ar is 3,4-Cl₂ C₆ H₃, R'is C₂ H₅, R" is CH₃, n Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-10-(2,4-dichlorophenyl)decan-3-ol [I; Ar is 2,4-Cl₂ C₆ H₃, R'is C₂ H₅, R" is CH₃, n is 2, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-10-(4-bromophenyl)decan-3-ol [I; Ar is 4-BrC₆ H₄, R' is C₂ H₅,R" is CH₃, n is 2, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-10-(4-fluorophenyl)decan-3-ol [I; Ar is 4-FC₆ H₄, R' is C₂ H₅,R" is CH₃, n is 2, Y is CH₂ CH₂ CH₂ CH₂ ];

3-methyl-10-(4-trifluoromethoxyphenyl)decan-3-ol [I; Ar is 4-F₃ COC₆ H₄,R' is C₂ H₅, R" is CH₃, n is 2, Y is CH₂ CH₂ CH₂ CH₂ ]; or

3-methyl-10-(4-trifluoromethylphenyl)decan-3-ol [I; Ar is 4-F₃ CC₆ H₄,R' is C₂ H₅, R" is CH₃, n is 2, Y is CH₂ CH₂ CH₂ CH₂ ].

By procedures analogous to those described above in Example 2,3-ethyl-6-(3,4-methylenedioxphenyl)-3-hexenyl iodide can be treated withthe lithium salt of 2-carbomethoxycyclohexane to afford2-carbomethoxy-2-[3-ethyl-6-(3,4-methylenedioxyphenyl)3-hexenyl]cyclohexanone,which can be hydrolyzed and decarboxylated to give2-[3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclohexanone [XIV; Aris 3,4-methylenedioxyphenyl, Y is C(C₂ H₅)═CHCH₂ CH₂, m is 2]. Thelatter can be further reacted with methylmagnesium bromide to produce1-methyl-2-[3-ethyl-6(3,4-methylenedioxyphenyl)-3-hexenyl]cyclohexanol[XV; Ar is 3,4-methylenedioxyphenyl, R' is CH₃, Y is C(C₂ H₅)═CHCH₂ CH₂,m is 2].

EXAMPLE 82-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclohexanone [XIV; Aris 3,4-methylenedioxyphenyl, Y is C(C₂ H₅)═CHCH₂ CH₂, m is 2].

A mixture of 20 g. (0.056 mole) of3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide and 21 g. (0.14mole) of 1-(N-pyrrolidyl)cyclohex-1-ene in 250 ml. of absolute ethanolwas heated at reflux for 20 hours under nitrogen. The reaction mixturewas concentrated in vacuo to a 150 ml. volume and added to 100 ml. ofwater. This mixture was heated to 80° C. for 70 minutes, then at refluxfor 10 minutes and cooled. It was then extracted three times with etherand the combined ether solutions washed successively with 5%hydrochloric acid, water, 5% sodium bicarbonate and water, dried overanhydrous magnesium sulfate and concentrated in vacuo. The residue waschromatographed on a column of 160 g. of silica gel, and the column waseluted with the pentane-benzene-chloroform-ether solvet series. Thefractions between pentane-benzene 8:2 and 100% chloroform brought outthe desired product as a yellow oil.

Anal. Calcd. for C₂₁ H₂₈ O₃ : C, 76.79; H, 8.59 Found: C, 77.08; H,8.97. IR (oil film) λ.sub.μ^(max) 3.44s + shldrs. (CH); 5.86s (C═O);6.15w, 6.24wm, 6.29w, 6.66mss, 6.73s, 6.94s, 6.94mss (unsat. arom, CH).NMR (20% CDCl₃, internal TMS) δ ppm (Ratio) 7.3(1/2) (CHCl₃); 6.7(3)(arom); 5.88(2) (O-CH₂ --O); 5.13(1) (═CH); 0.7-3.0 (22) (remainingaliphatic CH).

2-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclohexanone wasfound to be pesticidal against mealworm pupae (tenebrio) and rhodniusprolixus nymph at 10 micrograms per insect.

2-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclohexanone can betreated with allylmagnesium bromide according to the procedure ofExample 2, part (c) to give1-allyl-2-[3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclohexanol[XV; Ar is 3,4-methylenedioxyphenyl, Y is C(C₂ H₅)═CHCH₂ CH₂, R' is CH₂CH═CH₂, m is 2].

EXAMPLE 92-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclopentanone

[XIV; Ar is 3,4-methylenedioxyphenyl, Y is C(C₂ H₅ (═CHCH₂ CH₂, m is 1]was prepared from 26 g. of3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl iodide and 20 g. of1-(N-pyrrolidyl)cyclopent-1-ene according to the procedure describedabove in Example 8. There was thus obtained 8.6 g. of2-[3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclopentanone as alight amber oil.

Anal. Calcd. for C₂₀ H₂₆ O₃ : C 76.40; H, 8.34. Found: C, 76.52; H,8.33. IR (oil film) λ.sub.μ^(max) 3.45s + shldrs. (CH); 5.76s(cyclopentanone C═O); 6.11m (C═C); 6.24m, 6.66mss, 6.72s, 6.95mss(arom + CH). NMR (20% CDCl₃, internal TMS) δ ppm (Ratio) 6.72(3) (arom);5.93(2) (O--CH₂ --O), 5.17(1) (═CH); 0.7-2.8 (20) (aliph. CH incl. Metriplet).

2-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclopentanone wasfound to have a minimum inhibitory concentration in vitro against equinerhino virus of about 6 micrograms per milliliter.

2-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclopentanone wasfound to be pesticidal against yellow mealworm pupae (tenebrio) at 10micrograms per insect, dock beetle larvae at 5 micrograms per insect,yellow fever mosquito larvae at 6.6 ppm in water, and against rhodniusproxlixus nymph at 3 micrograms per insect.

2-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclopentanone can betreated with ethylmagnesium bromide according to the procedure ofExample 2, part (c) to give1-ethyl-2-[3-ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclopentanol[XV; Ar is 3,4-methylenedioxyphenyl, Y is C(C₂ H₅)═CHCH₂ CH₂, R' is C₂H₅, m is 1].

We claim:
 1. A compound of the formula ##STR12## wherein Y is selectedfrom the group consisting of ##STR13## R is hydrogen or lower-alkyl of 1to 4 carbon atoms; m is 1 or 2; andAr is phenyl or phenyl substituted by3,4-methylenedioxy or one or two monovalent substituents selected fromthe group consisting of lower-alkyl of 1 to 4 carbon atoms, lower-alkoxyof 1 to 4 carbon atoms, halogen, trifluoromethyl and trifluoromethoxy.2. A compound according to claim 1 wherein Ar is3,4-methylenedioxyphenyl and Y is C(R)═CHCH₂ CH₂. 3.2-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclohexanone,according to claim
 2. 4.2-[3-Ethyl-6-(3,4-methylenedioxyphenyl)-3-hexenyl]cyclopentanone,according to claim 2.